CN1012879B - Improved composite separation membranes and preparation and use thereof - Google Patents
Improved composite separation membranes and preparation and use thereofInfo
- Publication number
- CN1012879B CN1012879B CN88102874A CN88102874A CN1012879B CN 1012879 B CN1012879 B CN 1012879B CN 88102874 A CN88102874 A CN 88102874A CN 88102874 A CN88102874 A CN 88102874A CN 1012879 B CN1012879 B CN 1012879B
- Authority
- CN
- China
- Prior art keywords
- composite membrane
- separating layer
- volatile solvent
- film
- separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 121
- 239000002131 composite material Substances 0.000 title claims abstract description 89
- 238000000926 separation method Methods 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims description 8
- 238000000034 method Methods 0.000 claims abstract description 55
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 33
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 230000008569 process Effects 0.000 claims abstract description 16
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 43
- 230000002950 deficient Effects 0.000 claims description 42
- 239000000463 material Substances 0.000 claims description 35
- 230000035699 permeability Effects 0.000 claims description 33
- 238000012805 post-processing Methods 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 23
- 239000012466 permeate Substances 0.000 claims description 23
- 239000012530 fluid Substances 0.000 claims description 16
- 229920002492 poly(sulfone) Polymers 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005373 pervaporation Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 2
- 230000008961 swelling Effects 0.000 claims 2
- 238000010026 decatizing Methods 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 238000012856 packing Methods 0.000 claims 1
- 239000000725 suspension Substances 0.000 claims 1
- 238000001764 infiltration Methods 0.000 abstract description 12
- 230000007547 defect Effects 0.000 abstract description 11
- 230000008595 infiltration Effects 0.000 abstract description 10
- 230000000717 retained effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 69
- 239000000243 solution Substances 0.000 description 34
- 238000005516 engineering process Methods 0.000 description 26
- 239000000835 fiber Substances 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 15
- 239000001307 helium Substances 0.000 description 14
- 229910052734 helium Inorganic materials 0.000 description 14
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 230000009467 reduction Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 229920006221 acetate fiber Polymers 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- UDWPONKAYSRBTJ-UHFFFAOYSA-N [He].[N] Chemical compound [He].[N] UDWPONKAYSRBTJ-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- -1 and SPSF Polymers 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012510 hollow fiber Substances 0.000 description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- 239000004584 polyacrylic acid Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000000975 dye Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 229940029985 mineral supplement Drugs 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- 235000013619 trace mineral Nutrition 0.000 description 3
- 239000011573 trace mineral Substances 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- SWQJXJOGLNCZEY-BJUDXGSMSA-N helium-3 atom Chemical compound [3He] SWQJXJOGLNCZEY-BJUDXGSMSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920001230 polyarylate Polymers 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920002717 polyvinylpyridine Polymers 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical compound [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 210000002808 connective tissue Anatomy 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000009428 plumbing Methods 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000001612 separation test Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000011877 solvent mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000003319 supportive effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/362—Pervaporation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
- B01D65/106—Repairing membrane apparatus or modules
- B01D65/108—Repairing membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0229—Purification or separation processes
- C01B13/0248—Physical processing only
- C01B13/0251—Physical processing only by making use of membranes
- C01B13/0255—Physical processing only by making use of membranes characterised by the type of membrane
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/10—Specific pressure applied
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Combustion & Propulsion (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to process the composite membrane by volatile solvent with little or no additive in order to repair the defects of the separated folium, and then the membrane is dried by eliminating the solvent by evaporation; little involatile additive are still retained in the defects of the separated folium and seals the defect, which enhances the separation and infiltration character of the composite membrane.
Description
The present invention relates to the pellicle of separation fluid mixtures, specifically, the present invention relates to improve the stalling characteristic of composite membrane.The present technique field be can allowing fluid mixture selectively, liquid or gas, in a kind of component pass the method for obtaining required separation of the fluid that pellicle is regarded a kind of not only convenient as but also potential advantages are arranged.As the coml practical application, this film must can obtain the separation selectivity that allowed to the gas in the feed gas mixture or liquid.Meanwhile, also can obtain sufficiently high flow to the fluid components that passes this film selectively, or penetrance.
Pellicle has been widely used in counter-infiltration or the ultrafiltration technology, for example is used for the desalination of water.In reverse osmosis process, high pressure brine is contacted with pellicle, this film is transparent for water, then is not penetrable with respect to salt, promptly isolates dense salt solution and purer water thus.
Pellicle can also be used in more such separating technologies, and it relates to the variation of one or more component generation phases of separated mixture.Like this, charging and osmotic flow alternately change between the gas-liquid attitude, and its gas is present in a side of film.An example of this class technology is the pervaporation by film, is specially adapted to the solvent mixture fluid separation applications, and in this technology, liquid is present in the feed-side of film.Another example of this class technology is full structure (perstruction), and its liquid is present in the per-meate side of film.
In recent years, pellicle has been widely used in all gases to be separated, and the example of this application has gas to separate, and to reach recover hydrogen from refinery streams in the ammonia Purge gas, separating carbon dioxide and methane in the various operations reclaim as uncle's oil.
For carrying out this separation, the pellicle of wide variety of materials has been proposed in the present technique field.Having released so-called composite membrane, wherein is that the semipermeable membrane material that skim is suitable is superimposed on the lining with suitable porous, and for top said quite high flow is provided, this separating layer is got over Bao Yuehao.And said lining, to softness, permeable rete as thin as a wafer or on it additional coating play a supportive role.People such as Klass have done introduction to this structure of composite membrane in the US3616607 patent.People know the film for this separating technology, no matter be liquid or gas, all require film or separating layer to have the integrality of height.In gas separating technology, pervaporation is given in the technologies such as structure, if rete does not have any remaining hole or other defective, all can obtain best result obviously.On the other hand, in order to obtain needed high osmosis and high score, need to do rete thin as far as possible from productive rate.In this case, usually find remaining hole in the separation of thin layers of membrane module, the geometrical defect of forms such as tiny pin hole exists.In system membrane operations, all this class defective may be introduced in the film system such as spinning, casting, coated, plasticizing and this quasi-representative of system membrane module.
In the reverse osmosis deaslination technology in present technique field, when desalination is operated, along with constantly replenishing of Treatment Solution, the separating property of handling film will reduce usually.Membrane module will degenerate.Carrying out such processing usually is at the aqueous solution, consequently is dissolved in electrodeposition substance in this solution on a small quantity in the outer surface of this reverse osmosis membrane, and enters its outer hole.In people's such as Ganci US3808303 patent, and described such processing in other various lists of references,, will cause the essential size of improving reverse osmosis membrane surface characteristic and hole thereof significantly along with film separates the continuous increase of using.
In order to overcome the defective of gas separation membrane in preparation, in the patent of the US3980456 of Browall, introduced a kind of method, promptly seal coated the second time to cover by the caused many disadvantages of granule foreign to carrying out on the very thin films.The composite construction of Chu Liing is complicated in nature like this, and film stack is added on the support lining of porous.If the flow of its infiltration gas or permeability do not reduce in allowed limits, the selectivity of separation does not usually reach requirement.
The problem that has been found that the film defective is not only relevant with composite membrane, and relevant with the asymmetrical form of film.Distinguish this asymmetry film according to two different shape districts that exist in the membrane structure.One of them form district comprises that one can allow thin, the closely knit semi-permeable layer that a kind of component is passed through in the admixture of gas selectively.And another form district comprises that one is hanged down closely knit, with holes; The Support of non-selectivity, it play prevent film the thin layer district under pressure and the effect of breaking.People's such as Loeb US3133132 patent has been done introduction to this asymmetry film.As above-described composite membrane, when being used for the gas lock out operation, usually do not reach such purpose, and contain many defectives.Owing in the asymmetric membrane structure, have these defectives, so cause the gas fractional dose to reduce significantly.Having proposed the scheme of drawback that fix the defect causes in people's such as Henis the US4230463 patent, by ways that the people proposed such as Henis, is that limited amount remaining surface pore (is generally less than 10 of its total surface
-6) asymmetric membrane carry out coated to eliminate defective.The intrinsic separation factor of used coated material is littler than asymmetric membrane material.The separation factor that the film of resulting various ingredients presents is obviously greater than the intrinsic separation factor of coated material, and bigger than the separation factor that asymmetric membrane presented of coated not.
Following coating process is disclosed in the US4214020 of Ward patent, being about to a branch of hollow fibre impregnated in the coating solution, and then from the outside pressure is executed in the inside of this hollow fibre and order about coating solution and enter said fiber, to realize that hollow-fiber film spare outer surface is carried out coated.By people such as above-mentioned Henis in the technology described in its patent, this technology forms one pantostrat/coating because of causing on the hollow fibre outer surface, this technology is specially adapted to use has the coated material solution coated of high osmosis to have the asymmetric membrane of remaining hole to gas, with the high gas separation membrane of preparation selectivity.
Lee has introduced the treatment process that another kind of improvement has the asymmetric membrane stalling characteristic of remaining hole in the US4527999 patent.This technology is to cause under the different conditions of shrinking in surface pore, and right title cellulose acetate film is handled, so that the various characteristics of diffusion barrier is greatly improved.
Though the defective of film has been carried out the improvement of reparation property, and the existence of this class defective is still a problem, in order to obtain high seepage discharge, increase day by day for the needs of as thin as a wafer adventitia separating layer, it is serious that this problem then seems more.Conversely, the film separating layer as thin as a wafer that is provided is operated under condition of high voltage, because the existence of those defectives and the damage of separating layer can usually cause the reduction of film separation factor again.Therefore, in order to eliminate or reduce the problem of film defective, those skilled in the art person also need do more improvement.Especially need these defectives are repaired,, and the Penetration Signature of film is not had adverse influence so that can obtain higher stalling characteristic, thus the selectivity that in the lock out operation of various reality, can obtain, the permeability that can obtain again.
Side is mended these defectives, needs composite membrane is further improved, and carries out the stalling characteristic that coated can improve structure of composite membrane in common composite membrane, and has a kind of intrinsic retractility application that other form membrane structures are not had.Therefore can select separating layer according to desired separate use.The lining of said hollow fibre or other desired form then provides one to have hole, the supporting role of non-selectivity to said separating layer.Because composite membrane is understood by people day by day being used for the advantage that various gas-liquid separations operation showed, thus in the present technique field requirement develop the cry of all specific use composites will be more and more higher.As mentioned above, this development work comprises needed all stalling characteristics and high flow is combined that the overall performance that will separate and permeate in other words with all specific uses requires to do combination valuably.Along with the application to composite increases day by day, and in order fully to make total separation-infiltration require to adapt in various reality, commercial gas or separating in the application of liquid with composite membrane, provide one in order to the microscopic defect in the separating layer of repairing this class composite easily and effectively and the wide way of applicability has become more important.
One of purpose of the present invention provides one easily, the method for microscopic defect in the shutoff composite membrane separation of thin layers of applied range.
Second purpose of the present invention provide one improved can be near the composite membrane of the intrinsic stalling characteristic of coated material, and do not having tangible reduction aspect the Penetration Signature of separating layer.
The 3rd purpose of the present invention provides a kind of selectivity that both had, have infiltrative composite membrane again, and this film is specially adapted to gas, pervaporation or give the structure lock out operation.
These purposes of the present invention and other purpose will be described in detail hereinafter, and all features of its novelty will be described in additional claim specially.
Composite membrane is carried out post processing so that the defective in the shutoff composite membrane separation of thin layers, its concrete practice be with this film be that the pure volatile solvent that is added with or is not added with trace mineral supplement contacts basically, and then give dry till volatile solvent is gone up all removals substantially.Post-treatment solution can be imposed on composite membrane per-meate side or feed-side.The defective of composite membrane can be repaired with this post-processing approach, and this film can recover solid this stalling characteristic of separating layer basically fully like this, and the permeance property of this composite membrane does not have significantly or too big reduction.As be used for the separation of special gas or liquid mixture, and can both have selectivity to the feed mixture component that desire will be separated through the composite membrane of post processing, have permeability again.
The way with the composite membrane post processing that the objective of the invention is to be put down in writing in existing description and claim realizes, for having the various composite membrane compositions that special selectivity and permeability require concerning the highstrung various separating layers of defective and for being suitable for the operation of all gases or fluid separation applications, this post-processing approach all is easily and effectively, and is suitable for.The operating characteristics of this composite membrane is easy to obtain, and technology of the present invention can be implemented by embodiment preferred, this to a certain degree no matter the variation that is present in the defective in the composite membrane separating layer found how, can both be guaranteed various results' stability and repeated.
Find that surprisingly the defective in its closely knit separating layer can be with below the volatility post-treatment solution of introducing being carried out post processing and being made things convenient for and shutoff effectively.Such post processing recovers the intrinsic separating power of this film basically, and this composite membrane permeance property does not have undue reduction.Adopt aftertreatment technology of the present invention, can use composite membrane and membrane module, thereby the separating power that is used in the special separating layer material in this composite is fully used, not only make the acquisition selectivity but also can obtain permeability.
Technology of the present invention comprises makes the volatility post-treatment solution contact with the separating layer of composite membrane, and the film that this was handled gives drying subsequently, so as with treatment fluid from then in the film basic evaporative removal fully fall.This volatility post-treatment solution can comprise it being pure volatile solvent basically.Technical staff in the art understands, when application in practice of the present invention, this pure basically volatile solvent still contains the fixedness additive of trace, for example because purpose of the present invention floods oligomer, plasticizer or other compositions from film when contacting with film.Note that about this point the alleged composite membrane that contains remaining defective and handled by method described in the literary composition presents initial separation factor substantially herein, this just shows the tiny defect that denier is arranged and falls in this separating layer.The remaining aperture of separating layer is a dust level level, is no more than tens dusts at most.The amount of this class residual porosity also is seldom, the surface porosity factor of this separating layer, and promptly the ratio of the shared surface of hole and said separating layer total surface is generally less than 10
-7The mechanism of this class defective of shutoff also imperfectly understands effectively, but it seems that this defective is by the fixedness additive institute shutoff that is present in (ppm level concentration) in the volatile solvent system.Here said shutoff is the defective when this separating layer when being superimposed on the hole of porous lining, and this defective in the separating layer then can not provide a continuous communication composite membrane feed and the path of infiltration both sides, thereby causes this film optionally to reduce.
Selection requirement to used volatile solvent in the present invention's practice with regard to membrane material, has the non-solvent characteristic basically, or the expansion characteristics of appropriateness, to prevent the closely knit or film body distortion of pore structure.The term that usually is used for defining polymer and dissolution with solvents degree is " solubility parameter ", and it is defined as the square root of material cohesion energy density.With respect to the various membrane materials of making are non-solvents, and have the post processing dicyandiamide solution of appropriate expansion characteristics, and its solubility parameter is at least about than high or low 1.5 units of the solubility parameter of making membrane material that is used for processed film.Be suitable for that in the various different embodiments of the present invention there be representational volatile solvent: cyclohexane, isopropyl alcohol and water.
In the present invention's practice, used pure substantially volatile solvent effectively, but, usually wished in said solvent, to add the additive of a small amount of fixedness in order to improve the stable and repeated of its result.In the preferred embodiment of the invention, this post-treatment solution comprises extremely rare polymer solution.With regard to the object of the invention, the selectivity of this dissolved polymers can be more high or low than the selectivity of processed separating layer.But it should be noted that high its permeability of polymeric material of selectivity is low, especially separate in the application at gas.On the other hand, the polymeric material that selectivity is low typically demonstrates high permeability, as polyacrylic acid, and SPSF, polyvinyl pyridine or polyvinyl alcohol one class all can be used.The trace polymer concentration range generally is about 0.001%(by weight, 10ppm) to about 0.1%.When requiring to hang down selectivity, can use polymer as polysiloxanes or ethyl cellulose one class higher permeability, its concentration can increase to higher scope, and promptly about 0.001% to 1%.
Should be further understood that to have high stability and repeatability in order to ensure the gained result, the amount that adds trace mineral supplement in the post-treatment solution of volatile solvent changes very wide with regard to the scope of the invention.Can also enumerate few some polymer that are used for this volatile solvent system of some consumptions, as, polyacrylate, PEO, polyvinylpyrrolidone, polyvinyl pyridine, polyvinylamine and sulfonation polyarylate.
Add the additive of other type of trace by the concentration range of pointing out above in aftertreatment fluid, this is also within the scope of the invention.This class additive comprises fixedness liquid, has been found that it can block the defective of film effectively along with the evaporation of volatile solvent; The colloidal solid that suspends and the low molecular weight substance of dissolving are as plasticizer, antiplasticizer, various dyestuff and salt.This class material comprises low-molecular-weight polyalcohol, as glycerine; The dyestuff of red bright B one class of the pure and mild picture of ethylene glycol or Ji Wusan.In special use occasion, in order to improve the separating property of film, and use the post-treatment solution that contains above-mentioned additive agent mixture also at the row of the scope of the invention.In addition, aftertreatment technology of the present invention also can adopt independently some or continuous treatment step to realize, this independent process can adopt identical or different additives, or the independent process of several one or more additives of use combined, also can combine several independent processes of any additives that do not make.
In the time of in the composite membrane assembly being used in the separating technology that this film feed-side or per-meate side have liquid stream, for example, pervaporation or give structure (perstruction), character for any additives in the volatility post-treatment solution also must propose ask for something, the additive that is this occasion should not be dissolved in this class liquid stream, so that can get rid of from the defective of separating layer.
In another embodiment of the present invention, this aftertreatment technology is that the separating layer with composite membrane contacts with the post-treatment solution that contains the high concentration additive, uses the treated film of a volatility solvent wash then, is dried it at last again.If additive is a kind of nonvolatile liquid, itself can use this additive.In this scheme, this washing step is important.Owing to only before this drying steps, the surface of film is exposed in the volatile solvent, or is exposed in the volatile solvent that only contains a small amount of additive, generally could obtain the intrinsic stalling characteristic of film of getting well, and infiltration rate there is not too big loss.
Being to be noted that should be from being exposed to the surface of feed liquid separated flow one side, and for example, the feed side of film is handled the separating layer of this composite membrane, or is handled from the per-meate side of film.Another embodiment is from the feed side the whole surface of film to be contacted with post-treatment solution, with this separating layer is carried out post processing.Surface in order to ensure whole film contacts with said solution, by the feed side per-meate side of this film is applied different pressure, and this is useful generally speaking, and certainly, added pressure should not surpass the compacting yield point of processed membrane structure.
In another embodiment, be membrane module effectively to be handled from the per-meate side of film.In the time will using, for guaranteeing that membrane module is carried out stable continuous to be handled, be better than most between the per-meate side of film and the feed side under the condition of different pressures in addition, post-treatment solution is sent into the per-meate side of this film or membrane module.Like this when its supporting construction by this film per-meate side porous, will make that all defect face all contacts with post-treatment solution in the separating layer.Tackle used pressure differential and select, so then can avoid surpassing irreversible transformation point or its burst strength of film.Feed side at film vacuumizes, or pressurizes in the per-meate side of film, and keeps under atmospheric pressure in the feed side of film, or these means are combined, and can establish required pressure differential easily.Have found that the technology of separating layer being carried out post processing from per-meate side just can make remaining hole or other defect the separating layer obtain especially effectively shutoff, and can shutoff to the other parts of separating layer or porous lining.In addition, adopt this kind method also can carry out effective shutoff, be not deposited in a large number in the porous lining, also can under this separating layer, further not deposit and there are other materials to defective.Thus, separation requirement is improved, and productive rate lose seldom.
Aftertreatment technology of the present invention both can also can be handled composite membrane after assembling before the membrane module assembling.Yet, because such fact promptly may be introduced other defective this separating layer in the membrane module assembling process, so the weak effect that the membrane module after the effect of handling before the membrane module assembling generally will be compared assembling carries out post processing.For this reason, post processing generally is to carry out in the membrane separation device after assembling.Designed film device at least can fluid mixture in a kind of component separate effectively.This film device is made of a shell and the membrane module that is placed in one.This membrane module can be constructed to tubular that spiral twines, hollow fiber bundle, plate membrane module or the like, these membrane modules industrial be middlebrow.The membrane module of Jian Zaoing has a feed-side and permeates exit side in contrast to this like this.The housing of building can make the feed streams mixture contact with the feed-side of film.Be not provided with plumbing installation in order to remove part by the feed streams of this film and the infiltration gas removed individually by this film.Post-processing operation of the present invention can directly be carried out in above-mentioned housing, and membrane module is put into housing, or adopts another independent only being used to handle in the housing of membrane module and carry out.
So the those of ordinary skill in the present technique field is all known in implementing specific embodiments of the present invention the preferred volatile solvent or post-treatment solution will depend on processed composite membrane and for any given fluid separation operation condition and essential service ability.Volatile hydrocarbon, alcohols, water and fluorocarbon all are to implement preferred solvent among the present invention.It is non-interfering being used for the present invention's preferred solvent of enforcement and membrane material, and its boiling point is about 20 °-100 ℃.If use high boiling solvent, require then will increase the total cost of this aftertreatment technology for higher temperature and/or vacuumizing or the like.Certainly the objective of the invention is preferentially to select for use and can be easy to the solvent that evaporates at ambient temperature.
As mentioned above, the shutoff of microscopic defect can be the deposition that comes from the trace mineral supplement in the post processing dicyandiamide solution in the composite membrane separating layer, causes them to be adsorbed in the defective of separating layer, and with its obstruction.Yet, will cause in the unique defective that preferentially is deposited on separating layer substantially of shutoff material no matter its process mechanism how, has found that aftertreatment technology of the present invention.The composite membrane separating effect that carries out post processing by the present invention is very high, and in some cases, permeability has only very little reduction, or basic just not reduction.Conversely, when in the post processing solvent, during as additive, allowing to use low-permeability or impervious material.Like this, just the selectivity of separating layer can be brought up to the eigenvalue of separating layer material, and membranous permeation rate there is not too big reduction.
To be further described the present invention with each embodiment below, however, it is to be understood that these embodiment should not be formed in the restriction of the scope of the invention of being delimited in the claim that awaits the reply.
Embodiment 1
Prepare composite hollow fiber membrane with the hollow polysulfone fiber that is coated with acetate fiber, this hollow polysulfone fiber is with polysulfones glue spinning, quenching, and wash with general technology.(23 roll up in journal of applied as people such as Cabasso, the 1509-1525 page or leaf, 1979) in about " composite hollow fiber membrane " literary composition discuss like that, hollow polysulfone fiber can with this ternary solution of polysulfones, polyvinylpyrrolidone and dimethylacetylamide spin, wish polymer concentration total in the solution be 40-52%(by weight), the ratio of polysulfones/polyvinylpyrrolidone is 1.5-2.0.As everyone knows, for spinning process, sleeve spray yarn is easily, and the most handy 21 ℃ of water carry out outside quenching to fiber, and the quenching medium of fibrillar center is air preferably.Fiber after the washing is coated with after drying with acetate fiber coating drying and slaking again.For this purpose, by a feed liquid that is coated with that places the coated container,, before taking off from winder, allow it pass through curing oven the hollow fibre of drying, contact with maturing gas with dry air and higher temperature then by a drying oven.To this coated, dry and curing process has further to be introduced in people's such as Coplan US4467001 patent.The hollow fibre separation assembly is to utilize openend to be contained in the hollow fibre annular channels in the potting compound and be close to the collecting chamber that the openend of potting compound links to each other.The further details of this separation assembly see also people's such as Coplan US4207192 patent.When 100 pounds/square inch pressure, contain 10% helium/when nitrogen mixed gas stream is made separation test, find that the permeability of helium is 0.31ft
3/ ft
2Psi days, find that the selectivity between helium and the nitrogen is 52.Just as used herein, can know the ratio of the permeability of the selectivity of film or membrane module or the big infiltration component that separation factor is expressed as separated mixture with the permeability of less infiltration component.With cyclohexane this assembly is carried out post processing, promptly Aldrich level chemical reagent (ACS level reagent) is made volatile solvent.This embodiment any additives, the air feed side of assembly is filled full with cyclohexane, moistening film is contacted 15 minutes with cyclohexane, then, from assembly, discharge solvent, will be placed on 30 ℃ through the assembly of post processing is whole, in the vacuum of 28 inches of mercury dry 24 hours.The assembly of finding this post processing is 0.22ft to the infiltration rate of helium
3/ ft
2Psi days, the selectivity between helium and the nitrogen was increased to 7.0.
Embodiment 2
Method by embodiment 1 prepares the hollow fibre separation assembly, as the separating layer that is applied on the hollow polysulfone fiber, with 5% separates ratio down in 100psig with ethyl cellulose, and for example permeation volume/feed volume comes this assembly is tested with divided gas flow.The permeability of finding the oxygen of preferential infiltration is 0.21ft
3/ ft
2Separation factor between psi days oxygen and the nitrogen is 3.5.This assembly is with 5%(weight meter) glycerine (the Fisher Scientifi Certified ACS level) aqueous solution carries out post processing.This post-treatment solution is contacted with hollow fibre openend on the module permeate side, the feed side of film is imposed the vacuum 30 minutes of 28 inches of mercury, make this solution enter in the hollow fibre hole and the porous support structure of film in.To place 30 ℃ through the assembly of post processing, drying is 24 hours under the vacuum of 28 inches of mercury.It is used for divided gas flow so that this aftertreatment assembly is tested, and the components apart factor through handling has like this obtained effective increase, and to 3.7, the permeability of oxygen does not then have reduction.
Embodiment 3
Method by embodiment 1 prepares hollow thread fiber module, with acetate fiber as being applied to separating layer on the hollow polysulfone fiber.Gas permeation property with the pure helium of 100psig-this assembly of nitrogen stream test.Test finds that the permeability of helium is 0.58ft
3/ ft
2Psi days, the separation factor of helium and nitrogen was 6.3.With containing 0.05%(by weight) crosslinkable polysiloxanes Sylgard 184(Dow corning company) cyclohexane solution this assembly is carried out post processing.Its way is to be full of with Treatment Solution fully in the assembly feed-side, and the feed side of this assembly was applied 600psig pressure 30 minutes.Then, get rid of post-treatment solution, more whole assembly is placed 30 ℃, drying is 48 hours under the vacuum of 28 inches of mercury.Come the assembly of this post processing is tested again with pure helium-nitrogen stream.Know that through test the permeability of helium is 0.51ft
3/ ft
2Psi days, the separation factor between helium and the nitrogen was 104.The same aqueous solution with 0.01% polyacrylic acid (molecular weight is 50000) carries out post processing to this assembly also can make separation factor be improved, and permeability then has only very little reduction.
Embodiment 4
Handle acetate fiber hollow fibre composite with the aftertreatment technology of embodiment 3, but with 0.01%(by weight) aqueous solution of polyacrylic acid (molecular weight is 50000) is made post-treatment solution, polyacrylic acid is to have high score from characteristic, the representative substances of low-permeability characteristic.After treatment, the separation factor that makes helium-nitrogen brings up to 88 from 31, and to permeability not influence basically.
Embodiment 5
Prepare compound acetate fiber separation assembly on the hollow polysulfone fiber by the method for embodiment 1, method with embodiment 3, carry out post processing with crosslinkable polysiloxane solution from the assembly feed-side, but during handling, not from feed-side to the per-meate side of said film pressure differential in addition.After treatment, helium nitrogen separation factor is increased to 62 after the post processing from 18 of original assembly, and the permeability of helium only has and reduces slightly, reduces to 0.6ft from 0.8
3/ ft
2Psi days.
Embodiment 6
Will be as the separation assembly of forming by the acetic acid hollow fibre of embodiment 1 preparation, carry out post processing with method as embodiment 3, but post-treatment solution is to contain 0.5%(weight meter) dimethyl-phenyl siloxane copolymer (80-85% dimethyl, the 8-12% phenyl, molecular weight is 30000, Petrarch Systems company) cyclohexane solution.By after this method post processing, the helium of this assembly-nitrogen separation factor has clear improvement, from 11 bring up to 109 and post processing before the permeability 0.73ft of helium
3/ ft
2Comparing in psi days, at this moment is 0.50.
Embodiment 7
Press the foregoing description 1 preparation hollow fibre separation assembly, formed by being coated with on the hollow polysulfone fiber with the ethyl cellulose composite.When separation of air under 100psig, find that its oxygen-nitrogen separation factor is 3.4, the permeability of oxygen is 0.2ft
3/ ft
2Psi days.Making the feed-side and 5%(weight meter of hollow fiber module) glycerine water solution contacts.After half an hour, get rid of aftertreatment fluid from assembly, be dried in 60 ℃ air then, test finds that the oxygen/nitrogen separation factor of this aftertreatment assembly is 3.9, and the permeability of oxygen almost there is not variation.
Embodiment 8
Method by embodiment 1 prepares the hollow fibre separation assembly of being made up of the composite that scribbles cellulose acetate on the hollow polysulfone fiber.Pure helium-nitrogen stream with 100psig is tested the gas permeation property of this assembly, and the gas permeability that records helium through test is 1.8ft
3/ ft
2Psi days, the separation factor of helium-nitrogen was 9, and this assembly is with 1%(weight meter) aqueous solution of rhodamine B dyestuff (Aldrich chemical company) carries out post processing.This handles step and comprises with the feed-side of treatment fluid with membrane module and all being full of, then to the assembly feed-side pressure 30 minutes of 800psig in addition.From then on aftertreatment fluid is got rid of in the assembly again and gone, after a few minutes and drying, testing the permeability that records helium again is 1.5ft with ultra-pure water flushing feed-side
3/ ft
2Psi days, helium-nitrogen separation factor was 50.
From the foregoing description as can be seen: carry out post processing with the volatile solvent or the volatile solvent system that contain a small amount of additive by method of the present invention, the gas separation factor of composite membrane is improved, and gas permeability is not had obviously or too big reduction, but under some occasion, a bit reduce.
Those skilled in the art know that some details of aftertreatment technology of the present invention can do various changes and modification, but this is all within the scope that the claim of the present invention that application is awaited the reply delimited.They know also that available the inventive method shutoff is any and are suitable for the pervaporation of any actual industrial gas or give defective in the composite membrane separating layer of structure (prestructure), as the membrane material of separating layer with as the porous lining material of composite membrane supporting layer of the present invention can be any suitable material, as polymeric material or non-polymer material.Also can comprise multi-layer compound structure by said processing composite membrane herein, this film can have enzyme or other catalytic site, and this film can comprise an active transfer membrane.
In all these embodiment, all be to select separating layer according to the desired selectivity of fluid mixture to be separated, selected separating layer liner structure will combine consideration with convenient and its permeability characteristic.The example that preferentially is selected to the composite membrane separating layer polymeric material of handling according to the inventive method has: cellulose derivative, as ethyl cellulose and acetate fiber; Polyarylate is as polyphenylene oxides and polyacrylate, as polymethyl methacrylate.Though various known materials can be used as the porous support layer of this composite membrane as acetate fiber, polyphenylene oxides etc., the preferential material that is used to prepare composite membrane of the present invention is a polysulfones.
As above indication, the present invention can be conveniently used in the commercial operation of various reality, as the sky branch, recover hydrogen from the ammonia purified gas and in the refinery gas, the separation of the separating of the separating of carbon dioxide in the various operations and methane, helium and nitrogen, alcohol and water, wherein infiltration is the separation etc. of a moisture gas alcohol and water.Know that also the separating layer of handling according to the present invention generally contains very thin membrane material coating.In general, this separating layer thickness is generally 0.4 dust or following, and its preferred thickness range is the 0.02-0.2 Izod right side.
In each specific embodiments of the present invention, the stalling characteristic of composite membrane is to be determined by the separating layer of selecting.The present invention also makes the defective in the operation layer desirable method carry out effectively and shutoff selectively with convenience.In the main difficulty that runs into when overcoming the film that preparation has separating layer as thin as a wafer, the extensive utilization in various industrial fluids lock out operation contributes to composite membrane in the present invention.
Claims (28)
1, a kind of composite membrane that is suitable for gas separation, pervaporation (pervapor-ation) separation or full structure (perstructure) separation through post processing, comprise a separating layer and a porous supporting layer of determining the stalling characteristic of this film, this separating layer contains by the defective of a small amount of additive shutoff, this composite membrane through after the reason so that described defective is repaired, its mending course is mainly formed by following (a) with (b):
(a) described separating layer is contacted with the volatility post-treatment solution system that contains volatile solvent, this volatile solvent for this composite film material insoluble basically or have the appropriateness swellability, this solvent contains a small amount of non-volatile additive, promptly fills its defective when contacting with film;
(b) from this composite membrane, evaporate this volatile solvent, this a small amount of additive is still stayed in the defective, and play the effect of shutoff defective, make last handling process play the effect of the separating layer of repairing this composite membrane thus, improve its selectivity, and in use make selectivity and permeability obtain useful combination.
2, according to the composite membrane of claim 1, wherein last handling process carries out after this composite membrane is encased in separation assembly.
3, according to the composite membrane of claim 2, wherein this composite membrane is hollow fiber-shaped.
4, according to the composite membrane of claim 3, wherein the separating layer of this composite membrane comprises a kind of polymeric material.
5, according to the composite membrane of claim 4, wherein the solubility parameter of this volatile solvent soln system is at least than high or low about 1.5 units of the solubility parameter of this composite film material.
6, the method that is suitable for gas separation, pervaporation separation or full structure composite membrane for separation is promptly repaired in a kind of preparation, this film comprises a separating layer and a porous supporting layer of determining the stalling characteristic of this film, contain defectiveness in this separating layer, this method is mainly formed by following (a) with (b):
(a) this separating layer is contacted with the volatility post-treatment solution that contains volatile solvent, this volatile solvent does not dissolve substantially this composite film material or has an appropriate swelling character, this solvent contains the additive of a small amount of fixedness, promptly fills its defective when contacting with film;
(b) from this composite membrane, evaporate this volatile solvent, this a small amount of additive is still stayed in the defective, and play the effect of shutoff defective, make last handling process play the effect of the separating layer of repairing this composite membrane thus, improve its selectivity and in use make selectivity and permeability obtain useful combination.
7, according to the method for claim 6, wherein this volatile solvent soln system is to contact with this composite membrane separating layer of the separation assembly of packing into.
8, according to the method for claim 7, wherein this volatile solvent soln system contacts with the permeate side of this separation assembly, and it is poor to press to the feed side of separation assembly from permeate side.
9, method according to Claim 8, pressure differential wherein are that the feed side at this separation assembly vacuumizes and applies.
10, according to the method for claim 7, wherein this volatile solvent soln system is to contact with the feed-side of this separation assembly, and comprise exert pressure to permeate side from the feed-side of separation assembly poor.
11, according to the method for claim 10, wherein applying of this pressure differential is that permeate side at this separation assembly vacuumizes and realizes.
12, according to the method for claim 6, wherein a side from this composite membrane evaporates this volatile solvent.
13, according to the method for claim 6, wherein this composite membrane is hollow fiber-shaped.
14, according to the method for claim 13, wherein the separating layer of this composite membrane is to be made of polymeric material.
15, according to the method for claim 13, wherein this supporting layer is to be made of polysulfones.
16, according to the method for claim 6, wherein this volatile solvent soln system is main only is made up of volatile solvent, and this solvent comprises a spot of additive that leaching goes out from the material of this composite membrane itself.
17, according to the method for claim 6, wherein comprise a kind of volatile solvent and adding a spot of fixedness additive wherein in order to the volatile solvent soln system that contacts with this separating layer.
18, according to the method for claim 17, wherein this additive comprises dissolved polymers.
19, according to the method for claim 17, wherein this additive comprises the colloidal solid of suspension.
20, according to the method for claim 17, wherein this additive comprises dissolving, low-molecular-weight, nonvolatile additive basically.
21, according to the method for claim 6, wherein one after the other carry out and carry out repeatedly with step (a) with (b).
22, a kind of purposes of composite membrane of claim 1, this purposes is to be applied to separate by gas, pressure decatizing distribution separates or full structure is separated the less component of component from a kind of feed fluid mixture that permeability is big and permeability and separated, comprise and make this incoming mixture and be suitable for gas and separate, the feed-side of the composite membrane of pervaporation separation or full structure lock out operation contacts, obtain the big component of permeability respectively as permeate stream, reach the little component of permeability as non-permeate stream, this composite membrane has a separating layer and a porous supporting layer of determining this film stalling characteristic, and this composite membrane process following (a) and the process of (b) forming are carried out post processing:
(a) this separating layer is contacted with the volatility post-treatment solution system that contains volatile solvent, this volatile solvent does not dissolve or has the swelling character of appropriateness basically to composite film material, this solvent contains a small amount of fixedness additive, promptly fills its defective when it contacts with film;
(b) this volatile solvent is removed in evaporation from this composite membrane, this a small amount of additive is still stayed in the defective, and play the effect of shutoff defective, make last handling process play the effect of the separating layer of repairing this composite membrane thus, improve its selectivity, and in use make selectivity and permeability in separation process, obtain useful combination.
23, according to the method for claim 22, wherein this last handling process carries out after this composite membrane is encased in separation assembly.
24, according to the purposes of claim 22, wherein this composite membrane is hollow fiber-shaped.
25, according to the purposes of claim 22, wherein this feed mixture is the mixture that contains carbon dioxide and methane.
26, according to the purposes of claim 22, wherein this feed mixture contains the ammonia purge gas, and this permeate gas contains hydrogen.
27, according to the purposes of claim 22, wherein this feed mixture contains air, and this permeate gas contains aerobic.
28, according to the purposes of claim 22, wherein this feed mixture contains the mixture of alcohol and water, and this penetrant is a kind of moisture gas.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/035,783 US4767422A (en) | 1987-04-08 | 1987-04-08 | Composite separation membranes and the preparation and use thereof |
| US035,783 | 1987-04-08 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN88102874A CN88102874A (en) | 1988-11-30 |
| CN1012879B true CN1012879B (en) | 1991-06-19 |
Family
ID=21884760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN88102874A Expired CN1012879B (en) | 1987-04-08 | 1988-04-07 | Improved composite separation membranes and preparation and use thereof |
Country Status (7)
| Country | Link |
|---|---|
| KR (1) | KR920007858B1 (en) |
| CN (1) | CN1012879B (en) |
| AT (1) | ATE59574T1 (en) |
| BR (1) | BR8801656A (en) |
| DE (1) | DE3861341D1 (en) |
| GR (1) | GR3001385T3 (en) |
| MX (1) | MX165967B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2303436A4 (en) * | 2008-06-20 | 2012-08-15 | Univ Yale | Forward osmosis separation processes |
| KR101749158B1 (en) * | 2009-10-30 | 2017-07-04 | 오아시스 워터, 인크. | Osmotic separation systems and methods |
| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN108525524B (en) * | 2018-04-17 | 2021-05-14 | 上海穗杉实业股份有限公司 | Repairing device for hollow fiber gas separation membrane |
| CN115245747B (en) * | 2021-04-28 | 2024-02-27 | 天津膜天膜科技股份有限公司 | Leak repairing agent and method for repairing separation membrane |
-
1988
- 1988-04-07 KR KR1019880003968A patent/KR920007858B1/en not_active IP Right Cessation
- 1988-04-07 DE DE8888105552T patent/DE3861341D1/en not_active Expired - Lifetime
- 1988-04-07 AT AT88105552T patent/ATE59574T1/en active
- 1988-04-07 BR BR8801656A patent/BR8801656A/en active Search and Examination
- 1988-04-07 MX MX011039A patent/MX165967B/en unknown
- 1988-04-07 CN CN88102874A patent/CN1012879B/en not_active Expired
-
1991
- 1991-01-28 GR GR90400448T patent/GR3001385T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE3861341D1 (en) | 1991-02-07 |
| BR8801656A (en) | 1988-11-16 |
| CN88102874A (en) | 1988-11-30 |
| KR880012256A (en) | 1988-11-26 |
| MX165967B (en) | 1992-12-07 |
| GR3001385T3 (en) | 1992-09-11 |
| ATE59574T1 (en) | 1991-01-15 |
| KR920007858B1 (en) | 1992-09-18 |
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